CHAPTER 11: PROPERTIES OF LIQUIDS

Dr. Aimée TomlinsonChem1212

Solutions

Section 11.1

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What is a solution?

Solutions are formed from the addition of two species

Solute: dilute species

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Solvent: abundant species Solution

+ =

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Energy Changes & Solution Processes

Section 11.2

Universal Solution Rule

Like dissolves Like

Polar/ionic species require polar solvent

Nonpolar compounds require nonpolar solvents

Energy Steps in Solution Formation

Step 1: solute is separated into its individual components – endothernic, ΔH1 Step 2: IF between solvent molecules are broken – endothermic, ΔH2 Step 3: IF are generated between solute and solvent – exothermic, -ΔH3

On the left we have ΔHsolution < 0 Solute is completely solubleE.g. NaCl in water

1 2 3solutionH H H H

On the right we have ΔHsolution > 0 Solute is only partially solubleE.g. CaSO4 in water

Units of Concentration

Section 11.3

Measuring Solute to Solvent

moles of soluteM

L of solvent

Molarity

100%mass of solute

Mass percentmass of solution

Mass Percent/Percent by weight

A AA

A B tot

n n

n n n

Mole Fraction

moles of solutem

kg of solvent

Molality

6 or 10mg of solute g of solute

ppmkg of solvent g of solvent

Parts per Million, ppm

Factors that Affect Solubility

Section 11.4

Chemical Structure

MiscibilityHow well two substances mix together

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ImmiscibilityWhen two substances do not mix together

Partial MiscibilityHydrophilic component will mix in water while hydrophobic part won’tThe longer he hydrophobic chain the less miscible it will be in water

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Which one is more soluble in H2O?

CHCl3 CCl4

C6H11OH CH3OH

NaF MgO

Pressure

Primarily important for gases dissolved in solvent

Henry’s Law: gas solubility is directly proportional to gas pressureMathematically: Cgas = kHPgas

where Cgas is concentration of the gas in solution kH is Henry's constant for this gas in a particular solution

As we increase the pressure we increase the number of gaseous moles we can push into solutionThe opposite is also true, reduce P we reduce concentration

Example Calculation

Calculate the solubility of oxygen in water at 20C and an atmospheric pressure of 0.35 atm. The mole fraction of O2 in the air is 0.209 and kO2 = 1.3 x 10-3 mol/L*atm. (Answer: 9.5 x 10-5 M)

Temperature

we have already mentioned that we can increase T to force mixing between compounds

I should point out that if we are trying to mix polar and nonpolar species no amount of heat increase will ever cause miscibility

previously, I eluded to the idea that the sign ΔHsoln of is a predictor as to the solubility of two species

whille it is true to some extent there are many other factor which must also be consideredto be technically correct we must perform experiments to truly determine the extent of miscibility or immiscibility of two species

Physical Behavior of Solutions: Colligative Properties

Section 11.5

Here they are …

Vapor Pressure/Boiling Point Elevation

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Freezing Point Depression

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Osmotic Pressure

Vapor Pressures of Solutions

Section 11.6

Vapor Pressure & Temperature

VP increases as T increasesWhen T increases so do the molecular motions & kinetic E eventually allowing molecules to escape from l to g

RULE: to go from l → g, VP must equal atmospheric P

At higher elevations there is less atmospheric P so less heat is needed to boil (why water will boil below 100⁰C in Denver

Experiment – DI water vs Seawater

Over time, DI water is reduced as seawater increases

Water escapes from DI beaker faster

DI water liquifies back into the salt water beakerThe driving force is water wants to solvate salt Recall ion-dipole forces are stronger (more stable) than HbondingThis is why we use desicator packets to protect leather goods

TAKEHOME MESSAGE

The presence of a nonvolatile solute lowers the VP of a solvent

Calculating Vapor Pressure

We use Raoult’s Law: solution solvent solventP P

Example problem: What is the vapor pressure of water in a 50:50 mixture of glycerol (DC3H8O3 = 1.261 g/mL) and water at 25C (PH2O = 23.8 torr)? (Answer: Psoln = 19.1 torr)

Vapor Pressure for Volatile Mixtures

Petroleum IndustryOil is composed of a number of different hydrocarbonsThese all have similar but different boiling pointsThey can be separated through fractional distillation (see Section 11.10)

Raoult’s Law for a Volatile Mixture: All ideal solutions obey this Law

Example for Ideal Solution: Octane & Heptane

solution i ii

P P

They possess the following similarities:SizeBoiling pointIntermolecular forces (solute-solute,

solvent-solvent, and solute-solvent

Deviations from Raoult’s Law

Negative deviations: Solute-solvent interactions are stronger than solute-solute or solvent-solvent one

Positive deviations: Solute-solvent interactions are weaker than solute-solute or solvent-solvent one

Example of Volatile Mixture

At 20C, the VP of ethanol is 45 torr and the VP. of methanol is 92 torr. What is the VP at 20C of a solution prepared by mixing 75g of methanol and 25g of ethanol? (Answer: Psoln = 83 torr)

Boiling Pt Elevation & Freezing Pt Depression

of Solutions

Section 11.7

Reminder: VP & Bpt Relationship

At boiling VP = Patm

Recall Seawater ExperimentThe salt lowered VP of water

This makes a larger energy gap to reach Patm

A larger gap means more heat required to boil

TAKEHOME MESSAGE II

The presence of a nonvolatile solute raises the boiling point of a solution

Boiling Point Elevation

Boiling point line is shifted when nonvolatile solute is added

Mathematically: where ΔTb is the change in boiling point, Kb is a

constant, and msolute is the molality of the solute in solution

b b soluteT K m

Example Bpt Elevation Problem

If the boiling point of a sample is 2.3 Celcius above the boiling point of pure water, what is the molality of NaCl in the sample?(Answer: 4.4 m NaCl)

, 0.52 /ob waterK C kg mol

Freezing Point Depression

Similar to Boiling Point

Salt melts ice by lowering the VP

This makes the freezing point lower

Lowering freezing point ends up allowing water to melt above its normal freezing point T

Mathematically: f f soluteT K m www.uniongas.com/images/meltingIcetechnology.jpg

Osmosis & Osmotic Pressure

Section 11.8

Osmosis

When solvent passes through a semipermeable membrane to balance the solute concentrations on each side of the membrane

Osmotic Pressure

amount of pressure needed to stop the solvent from flowing to the more concentrated side of a semipermeable membrane

http://nanotech.sc.mahidol.ac.th/genchem/liquid1/osmo.jpg

0.0821 L atmmol KMRT R

M molarity T in K

Easy Example Problem

Calculate the osmotic pressure across a semipermeable membrane separating seawater (1.14 M) from a solution of normal saline (0.31 M) at a T = 20C. (Answer: 20 atm)

Difficult Example Problem

A solution was made by dissolving 5.00 mg of hemoglobin in water to give a final volume of 1.00 mL. The osmotic pressure of this solution was 1.91 x 10-3 atm at 25 oC. Calculate the molar mass of hemoglobin. (Answer: 6.41 x 104 g/mol)

Reverse Osmosis

solvent is pumped through semi-impermeable membrane at a pressure greater than leaving behind solute particles

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Used to purify water

Applications & Fractional Distillation

Section 11.9 & 11.10

Fractional Distillation

Mixtures are separated by this method

Lower bpt components boil first & collected at the top (e.g. petrol)

Higher bpt special boil last and are collected at the bottom (e.g. crude oil)

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Electrolytic Solutions

Section

Reminder: What are Electrolytes?

They are solutions possessing ions

They allow water to conduct electricity

Strong electrolytes dissolve completely (e.g. NaCl)

Weak electrolytes only partially dissolve (e.g. CaSO4)

Non-electrolytes do not dissolve inwater at all and are not ionic (e.g. glycerol)

van’t Hoff Factor, i

Used to indicated the strength of the electrolyte

moles of particles in solutioni

moles of solute dissolved

What is i for the following?

LiF

What is i for the following?

MgO

What is i for the following?

Calcium Phosphate

True Colligative Equations

Electrolytes DO matter!!!

Example Problem

The van't Hoff factor for a 0.05 m solution of magnesium sulfate is 1.3. What is the freezing point of the solution?(Answer: ΔTf = -0.12⁰C)

f, 1.86 /owaterK C kg mol

If the boiling point of a sample is 2.3 Celcius above the boiling point of pure water, what is the molality of NaCl in the sample? (Answer: 2.2 m NaCl)

Bpt Example with i

Conceptual Problem

For the list of compounds below rank them in order of increasing boiling point, freezing point, osmotic pressure and vapor pressure. Assume a 1.0M solution for each reagent and complete dissociation where applicable. C11H22O11, KBr, Li2SO4

First, we determine i for each compound.

C11H22O11 → i = 1

KBr → i =2

Li2SO4→ i = 3

Conceptual Problem

For the list of compounds below rank them in order of increasing boiling point, freezing point, osmotic pressure and vapor pressure. Assume a 1.0M solution for each reagent and complete dissociation where applicable. C11H22O11, KBr, Li2SO4

We use i,C11H22O11(i = 1), KBr(i =2), Li2SO4( i = 3), and the mathematical equation for each trend

Boiling Point Trend:

C11H22O11 < KBr < Li2SO4

b b soluteT iK m

Conceptual Problem

For the list of compounds below rank them in order of increasing boiling point, freezing point, osmotic pressure and vapor pressure. Assume a 1.0M solution for each reagent and complete dissociation where applicable. C11H22O11, KBr, Li2SO4

We use i,C11H22O11(i = 1), KBr(i =2), Li2SO4( i = 3), and the mathematical equation for each trend

Freezing Point Trend:

Li2SO4 < KBr < C11H22O11

f f soluteT iK m

Conceptual Problem

For the list of compounds below rank them in order of increasing boiling point, freezing point, osmotic pressure and vapor pressure. Assume a 1.0M solution for each reagent and complete dissociation where applicable. C11H22O11, KBr, Li2SO4

We use i,C11H22O11(i = 1), KBr(i =2), Li2SO4( i = 3), and the mathematical equation for each trend

Osmotic Pressure Trend:

C11H22O11 < KBr < Li2SO4

iMRT

Conceptual Problem

For the list of compounds below rank them in order of increasing boiling point, freezing point, osmotic pressure and vapor pressure. Assume a 1.0M solution for each reagent and complete dissociation where applicable. C11H22O11, KBr, Li2SO4

We use i,C11H22O11(i = 1), KBr(i =2), Li2SO4( i = 3), and the mathematical equation for each trend

Vapor Pressure Trend:

Li2SO4 < KBr < C11H22O11

lnso solvent solvent

solventsolvent

solute solvent

P P

n

i n n

Example VP Problem with i

What is the VP of a solution containing 1L of water and 500 g of NaCl? (at 25⁰C the VP of water is 23.8 torr) (Answer: 18.2 torr)